JP2001270891A - Phosphoric ester having benzoxazine ring - Google Patents
Phosphoric ester having benzoxazine ringInfo
- Publication number
- JP2001270891A JP2001270891A JP2000084468A JP2000084468A JP2001270891A JP 2001270891 A JP2001270891 A JP 2001270891A JP 2000084468 A JP2000084468 A JP 2000084468A JP 2000084468 A JP2000084468 A JP 2000084468A JP 2001270891 A JP2001270891 A JP 2001270891A
- Authority
- JP
- Japan
- Prior art keywords
- substituted
- benzoxazine ring
- dihydro
- phenyl group
- substituted phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、３，４−ジヒドロ
−３置換−１，３−ベンゾオキサジン環を有するリン酸
エステルに関する。The present invention relates to a phosphoric ester having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring.
【０００２】[0002]
【従来の技術】樹脂系材料は、成形性が優れており種々
の用途に向けた成形物として広く使用されている。しか
し、樹脂系材料の多くは易燃性であり、通信用、民生
用、産業用等の材料として利用するには、より優れた耐
熱性、難燃性が要求されつつある。従来、難燃性能向上
のために塩素系、臭素系のハロゲン系難燃剤やＳｂ
2Ｏ3、Ｓｂ2Ｏ5等の難燃助剤を併用しなければならず、
ハロゲン系難燃剤の熱分解時の有毒ガスの発生などが環
境面などにおいて問題点を有していた。また、樹脂系材
料の難燃性能向上のためにハロゲン系難燃剤に代わって
リン系化合物などのノンハロゲン系難燃剤が提案されて
いるが、これらは、添加量によっては、樹脂材料のガラ
ス転移温度を低下させたり、組成物の熱膨張率が高くな
るなどの問題点を有していた。2. Description of the Related Art Resin-based materials have excellent moldability and are widely used as molded articles for various uses. However, many resin-based materials are easily flammable, and are required to have better heat resistance and flame retardancy when used as materials for communication, consumer use, industrial use, and the like. Conventionally, chlorine-based and bromine-based halogen-based flame retardants and Sb
Flame retardant aids such as 2 O 3 and Sb 2 O 5 must be used together,
The generation of toxic gases during the thermal decomposition of halogen-based flame retardants has had problems in environmental aspects and the like. Non-halogen flame retardants such as phosphorus compounds have been proposed in place of halogen flame retardants in order to improve the flame retardancy of resin materials. And the thermal expansion coefficient of the composition becomes high.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、樹脂系材料
の難燃剤として使用可能なリン酸エステル化合物を提供
することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a phosphate compound which can be used as a flame retardant for a resin material.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討を重ねた結果、新規化合物で
ある３，４−ジヒドロ−３置換−１，３−ベンゾオキサ
ジン環を有するリン酸エステルが、樹脂系材料などの有
するガラス転移温度、熱膨張率などの性能を低下するこ
となく難燃性能を向上させるノンハロゲン系難燃剤とな
ることを見出し、本発明を完成するに至った。すなわ
ち、本発明は、 １． 下記一般式（１）で示される３，４−ジヒドロ−
３置換−１，３−ベンゾオキサジン環を有するリン酸エ
ステル、Means for Solving the Problems The present inventors have made intensive studies in order to solve the above problems, and as a result, have found that a novel compound, a 3,4-dihydro-3-substituted-1,3-benzoxazine ring, has been obtained. Has been found to be a non-halogen flame retardant that improves the flame retardancy without lowering the glass transition temperature, coefficient of thermal expansion, etc. of the resinous material, and has led to the completion of the present invention. Was. That is, the present invention provides: 3,4-dihydro- represented by the following general formula (1)
A phosphate ester having a trisubstituted-1,3-benzoxazine ring,
【０００５】[0005]
【化３】 Embedded image
【０００６】（式中、Ｔ１、Ｔ２、Ｔ３は、各々独立に
無置換もしくは置換フェニル基、又は炭素数１〜１０の
脂肪族炭化水素残基を表する。Ｔ１、Ｔ２、Ｔ３の少な
くとも１つが３，４−ジヒドロ−３置換−１，３−ベン
ゾオキサジン環を有する置換フェニル基である。） ２．上記１記載のリン酸エステルの３，４−ジヒドロ−
３置換−１，３−ベンゾオキサジン環を有する置換フェ
ニル基が下記一般式（２）または（３）で示されるリン
酸エステル、(Wherein T1, T2, and T3 each independently represent an unsubstituted or substituted phenyl group, or an aliphatic hydrocarbon residue having 1 to 10 carbon atoms. At least one of T1, T2, and T3 represents It is a substituted phenyl group having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring.) 3,4-dihydro- of the phosphoric ester according to the above 1
A substituted or unsubstituted phenyl group having a 3-substituted-1,3-benzoxazine ring represented by the following general formula (2) or (3):
【０００７】[0007]
【化４】 Embedded image
【０００８】（式中、ａは１又は２、ｃは０又は１であ
り、かつａ＋ｃ＝２であり、Ｒ１は無置換もしくは置換
のフェニル基、メチル基又はシクロヘキシル基を表し、
Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６は各々独立に水素又は炭
素数１〜１０のアルキル基を表す。）である。以下、本
発明について、詳細に説明する。本発明の３，４−ジヒ
ドロ−３置換−１，３−ベンゾオキサジン環を有するリ
ン酸エステルは、下記一般式（１）で示されるリン酸エ
ステルである。Wherein a is 1 or 2, c is 0 or 1, and a + c = 2, and R1 represents an unsubstituted or substituted phenyl group, methyl group or cyclohexyl group;
R2, R3, R4, R5, and R6 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms. ). Hereinafter, the present invention will be described in detail. The phosphate ester having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring of the present invention is a phosphate ester represented by the following general formula (1).
【０００９】[0009]
【化５】 Embedded image
【００１０】上記式中、Ｔ１、Ｔ２、Ｔ３は、各々独立
に無置換もしくは置換フェニル基、又は炭素数１〜１
０、好ましくは樹脂系材料への相溶性から、１〜５の脂
肪族炭化水素残基を表す。ただし、Ｔ１、Ｔ２、Ｔ３の
少なくとも１つが３，４−ジヒドロ−３置換−１，３−
ベンゾオキサジン環を有する置換フェニル基である。本
発明において、３，４−ジヒドロ−３置換−１，３−ベ
ンゾオキサジン環を有する置換フェニル基の例を、下記
化６に示す。In the above formula, T1, T2 and T3 each independently represent an unsubstituted or substituted phenyl group, or a group having 1 to 1 carbon atoms.
0, preferably 1 to 5 aliphatic hydrocarbon residues in view of compatibility with the resin material. Provided that at least one of T1, T2 and T3 is 3,4-dihydro-3-substituted-1,3-
It is a substituted phenyl group having a benzoxazine ring. In the present invention, an example of a substituted phenyl group having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring is shown in the following chemical formula 6.
【００１１】[0011]
【化６】 Embedded image
【００１２】上記式中、ａは１又は２、ｃは０又は１で
あり、かつａ＋ｃ＝２であり、Ｒ1は無置換もしくは置
換のフェニル基、メチル基又はシクロヘキシル基を表
し、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６は各々独立に水素又
は炭素数１〜１０、好ましくは樹脂系材料への相溶性か
ら、１〜５のアルキル基を表す。） 本発明の３，４−ジヒドロ−３置換−１，３−ベンゾオ
キサジン環を有するリン酸エステル化合物は、製造やコ
スト面から好ましくは下記一般式（４）で示されるリン
酸エステルである。In the above formula, a is 1 or 2, c is 0 or 1, and a + c = 2, R 1 represents an unsubstituted or substituted phenyl group, methyl group or cyclohexyl group, and R 2, R 3 , R4, R5, and R6 each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 5 in view of compatibility with the resin material. The phosphate ester compound having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring of the present invention is preferably a phosphate ester represented by the following general formula (4) from the viewpoint of production and cost.
【００１３】[0013]
【化７】 Embedded image
【００１４】（式中、ａ＋ｂ＋ｃ＝３、ａは１〜３の
整数、ｂは０〜２の整数、ｃは０〜２の整数であり、Ｒ
１は、無置換もしくは置換のフェニル基、メチル基、又
はシクロヘキシル基であり、Ｒ２、Ｒ３、Ｒ４、Ｒ５、
Ｒ６ は各々独立に水素又は炭素数１〜１０、好ましく
は１〜５のアルキル基である。） ３，４−ジヒドロ−３置換−１，３−ベンゾオキサジン
環を有するリン酸エステルの製造方法の一例を以下に示
す。１，３−ベンゾオキサジン環を構成するには、フェ
ノール類、アミン、ホルムアルデヒドから合成すること
が知られており、本発明の難燃剤も対応するフェノール
性水酸基を有するリン酸エステル、アミン及びホルムア
ルデヒドから合成することができる。(Where a + b + c = 3, a is 1 to 3)
An integer, b is an integer of 0 to 2, c is an integer of 0 to 2,
1 is an unsubstituted or substituted phenyl group, methyl group, or cyclohexyl group, and R2, R3, R4, R5,
R6 is each independently hydrogen or an alkyl group having 1 to 10, preferably 1 to 5 carbon atoms. An example of a method for producing a phosphate ester having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring is shown below. It is known that a 1,3-benzoxazine ring is synthesized from phenols, amines and formaldehyde. The flame retardant of the present invention is also prepared from a corresponding phenolic hydroxyl group-containing phosphate ester, amine and formaldehyde. Can be synthesized.
【００１５】具体的には、２段階の合成工程により得る
ことができる。まず、最初の工程として、アミンとホル
ムアルデヒドを２０℃以下の低温条件下で撹拌させる。
このとき、有機溶媒で希釈した溶液を使用することが、
反応をすみやかに進行させるために好ましい。使用する
有機溶媒としては、エタノール、１，４−ジオキサン、
ジエチレングリコールなどがあげられる。また、反応温
度を２０℃より高い温度にて行うと、アミンとホルムア
ルデヒドとの重合反応が進行し目的化合物が得られな
い。その後、２段階目の工程としてフェノール性水酸基
を有する化合物をアミンとホルムアルデヒド混合溶液に
添加し３０℃以上の温度にて撹拌することにより目的化
合物が合成される。このとき、温度は、３０℃以上であ
ることが必要であるが、反応性や使用する有機溶媒の選
定から１００℃〜２００℃の反応温度にて行うことが好
ましい。Specifically, it can be obtained by a two-stage synthesis process. First, as the first step, the amine and formaldehyde are stirred at a low temperature of 20 ° C. or less.
At this time, using a solution diluted with an organic solvent,
It is preferable for the reaction to proceed promptly. Examples of the organic solvent used include ethanol, 1,4-dioxane,
And diethylene glycol. If the reaction is carried out at a temperature higher than 20 ° C., the polymerization reaction between the amine and formaldehyde proceeds and the target compound cannot be obtained. Then, as a second step, a compound having a phenolic hydroxyl group is added to a mixed solution of amine and formaldehyde, and the mixture is stirred at a temperature of 30 ° C. or higher, whereby the target compound is synthesized. At this time, the temperature needs to be 30 ° C. or higher, but it is preferable to perform the reaction at a reaction temperature of 100 ° C. to 200 ° C. from the viewpoint of reactivity and selection of an organic solvent to be used.
【００１６】その後、一般的な有機化合物を単離する方
法にて単離することが可能である。具体例としては、反
応溶液中の有機溶媒を留去した残留物の再結晶や抽出方
法などがあげられる。また、使用するアミンとしては一
価アミンを用いても、多価アミンを用いても良い。アミ
ンの具体例として、一価アミンとしてアニリン、トルイ
ジン、メチルアミン、シクロヘキシルアミンなどがあげ
られ、多価アミンとしては、二価アミンとしてパラフェ
ニレンジアミンなどがあげられ、三価以上のアミンとし
てはトリアミノナフタレンやトリアミノアントラセンな
どがあげられる。Thereafter, it is possible to isolate a general organic compound by a method for isolating it. Specific examples include a method of recrystallization and extraction of a residue obtained by distilling an organic solvent from a reaction solution. Further, as the amine to be used, a monovalent amine or a polyvalent amine may be used. Specific examples of the amine include aniline, toluidine, methylamine, and cyclohexylamine as the monovalent amine, paraphenylenediamine as the divalent amine, and triamine as the trivalent or higher amine. Examples include aminonaphthalene and triaminoanthracene.
【００１７】フェノール性水酸基を有するリン酸エステ
ルとアミン及びホルムアルデヒドとの組み合わせは、用
途により任意に選択することが可能であるが、生産性や
コスト面からリン酸エステル構造単位中に３，４−ジヒ
ドロ−３置換−１，３−ベンゾオキサジン環を１個有す
る構造が得られることが好ましく、１個のフェノール性
水酸基を有するリン酸エステルと一価アミンとホルムア
ルデヒドの組み合わせが好ましい。また、難燃性を向上
させるためには、アミンは芳香族アミンを用いることが
好ましい。The combination of a phosphoric acid ester having a phenolic hydroxyl group with an amine and formaldehyde can be arbitrarily selected depending on the intended use, but from the viewpoint of productivity and cost, 3,4- Preferably, a structure having one dihydro-3-substituted-1,3-benzoxazine ring is obtained, and a combination of a phosphoric ester having one phenolic hydroxyl group, a monovalent amine and formaldehyde is preferable. In order to improve the flame retardancy, it is preferable to use an aromatic amine as the amine.
【００１８】３，４−ジヒドロ−３置換−１，３−ベン
ゾオキサジン環を有するリン酸エステルは、赤外吸収ス
ペクトル法、高分解能固体核磁気共鳴スペクトル法、熱
分解ガスクロマトグラフィー等の方法を用いて樹脂組成
を解析することができる。本発明のベンゾオキサジン環
を有するリン酸エステルは、加熱すると単独重合する。
本発明のリン酸エステルは、優れた耐熱性、難燃性を有
し、特に芳香族環を有する樹脂との組成物において優れ
た耐熱性、難燃性を示し、電気産業、電子産業、建築産
業、宇宙・航空機産業等の分野に向けた非ハロゲン難燃
剤、耐熱材料等に用いることができる。Phosphate esters having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring can be obtained by methods such as infrared absorption spectroscopy, high-resolution solid-state nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography. Can be used to analyze the resin composition. The phosphate ester having a benzoxazine ring of the present invention undergoes homopolymerization when heated.
The phosphoric acid ester of the present invention has excellent heat resistance and flame retardancy, and particularly exhibits excellent heat resistance and flame retardancy in a composition with a resin having an aromatic ring. It can be used for non-halogen flame retardants, heat-resistant materials, etc. for the fields of industry, space and aircraft industries.
【００１９】[0019]
【発明の実施の形態】以下、実施例に基づき、本発明を
説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
【００２０】[0020]
【実施例１】（３，４−ジヒドロ−３置換−１，３−ベ
ンゾオキサジン環を有するリン酸エステル）ジオキサン
にて希釈した５０ｗｔ％アニリン溶液を氷冷し３７ｗｔ
％ホルムアルデヒド水溶液を１０℃以下にて滴下した。
その後、氷冷を取り除き、３０分間、室温下にて撹拌し
た後、ジオキサンに溶解させたレゾルシルジフェニルホ
スフェート（味の素（株）製 ＲＤＰ）５０ｗｔ％を室
温にて滴下した。これらの混合物を約６時間加熱環流を
行った後、ジオキサン溶媒を留去し薄黄色の残留物が得
られた。これらをジエチルエーテル中に溶解し３規定水
酸化ナトリウム溶液で数回洗浄した後、水で洗浄しジエ
チルエーテル溶媒を留去することにより得られた。な
お、アニリン：ホルムアルデヒド：レゾルシルジフェニ
ルホスフェートのモル比は１：２：１となる仕込み比に
て行った。下記化８に示すリン酸エステルが得られた。Example 1 (Phosphate ester having 3,4-dihydro-3-substituted-1,3-benzoxazine ring) A 50 wt% aniline solution diluted with dioxane was cooled on ice to 37 wt%.
% Formaldehyde aqueous solution was added dropwise at 10 ° C or lower.
Thereafter, ice-cooling was removed, and the mixture was stirred at room temperature for 30 minutes, and then 50 wt% of resorcil diphenyl phosphate (RDP manufactured by Ajinomoto Co., Ltd.) dissolved in dioxane was added dropwise at room temperature. After the mixture was heated and refluxed for about 6 hours, the dioxane solvent was distilled off to obtain a pale yellow residue. These were dissolved in diethyl ether, washed several times with a 3N sodium hydroxide solution, then washed with water, and the diethyl ether solvent was distilled off. The reaction was carried out at a charging ratio of aniline: formaldehyde: resorcildiphenylphosphate of 1: 2: 1. The phosphoric ester represented by the following formula 8 was obtained.
【００２１】[0021]
【化８】 Embedded image
【００２２】なお、上記化８に示すリン酸エステルの構
造の同定は、Ｈ−ＮＭＲおよび赤外線吸収スペクトルに
て行った。赤外線吸収スペクトルを図１に示す。ＮＭＲ
の測定は日本電子（株）製（ＥＸ−２７０）の測定装置
を用いて行った。重水素化溶媒はクロロホルムを使用し
た。 ４，６ｐｐｍ ｓ ２Ｈ：ベンゾオキサジン構造メチレ
ンプロトン ５．４ｐｐｍ ｓ ２Ｈ：ベンゾオキサジン構造メチレ
ンプロトン ６．６〜７．４ｐｐｍ ｂｒ １８Ｈ：フェノール環プ
ロトンThe structure of the phosphoric ester shown in Chemical formula 8 was identified by H-NMR and infrared absorption spectrum. FIG. 1 shows the infrared absorption spectrum. NMR
Was measured using a measuring device manufactured by JEOL Ltd. (EX-270). Chloroform was used as the deuterated solvent. 4,6 ppm s 2H: methylene proton of benzoxazine structure 5.4 ppm s 2H: methylene proton of benzoxazine structure 6.6 to 7.4 ppm br 18H: phenol ring proton
【図１】本発明の実施例１で得られたリン酸エステルの
赤外線吸収スペクトル図である。FIG. 1 is an infrared absorption spectrum of a phosphoric ester obtained in Example 1 of the present invention.
Claims (2)
ヒドロ−３置換−１，３−ベンゾオキサジン環を有する
リン酸エステル。 【化１】 （式中、Ｔ１、Ｔ２、Ｔ３は、各々独立に無置換もしく
は置換フェニル基、又は炭素数１〜１０の脂肪族炭化水
素残基を表す。但し、Ｔ１、Ｔ２、Ｔ３の少なくとも１
つが３，４−ジヒドロ−３置換−１，３−ベンゾオキサ
ジン環を有する置換フェニル基である。）1. A phosphate ester having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring represented by the following general formula (1). Embedded image (In the formula, T1, T2, and T3 each independently represent an unsubstituted or substituted phenyl group, or an aliphatic hydrocarbon residue having 1 to 10 carbon atoms, provided that at least one of T1, T2, and T3 represents
One is a substituted phenyl group having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring. )
−ジヒドロ−３置換−１，３−ベンゾオキサジン環を有
する置換フェニル基が下記一般式（２）または（３）で
示される置換フェニル基であるリン酸エステル。 【化２】 （式中、ａは１又は２、ｃは０又は１であり、かつａ＋
ｃ＝２であり、Ｒ１は無置換もしくは置換のフェニル
基、メチル基又はシクロヘキシル基を表し、Ｒ２、Ｒ
３、Ｒ４、Ｒ５、Ｒ６は各々独立に水素又は炭素数１〜
１０を表す。）2. The 3,4 of the phosphate ester according to claim 1.
A phosphate ester in which the substituted phenyl group having a dihydro-3-substituted-1,3-benzoxazine ring is a substituted phenyl group represented by the following general formula (2) or (3). Embedded image Wherein a is 1 or 2, c is 0 or 1, and a +
c = 2, R1 represents an unsubstituted or substituted phenyl group, methyl group or cyclohexyl group;
3, R4, R5, and R6 each independently represent hydrogen or 1 to carbon atoms.
Represents 10. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000084468A JP2001270891A (en) | 2000-03-24 | 2000-03-24 | Phosphoric ester having benzoxazine ring |
Applications Claiming Priority (1)
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| JP2000084468A JP2001270891A (en) | 2000-03-24 | 2000-03-24 | Phosphoric ester having benzoxazine ring |
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| JP2001270891A true JP2001270891A (en) | 2001-10-02 |
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| JP2000084468A Withdrawn JP2001270891A (en) | 2000-03-24 | 2000-03-24 | Phosphoric ester having benzoxazine ring |
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| EP2036912A1 (en) | 2007-09-11 | 2009-03-18 | Samsung Electronics Co., Ltd. | Phosphorous containing benzoxazine-based monomer, polymer thererof, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell employing the same |
| US8034508B2 (en) | 2005-09-03 | 2011-10-11 | Samsung Sdi Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| US8148028B2 (en) | 2006-05-29 | 2012-04-03 | Samsung Sdi Co., Ltd. | Polybenzoxazines, electrolyte membrane comprising the same, and fuel cell employing the electrolyte membrane |
| US8188210B2 (en) | 2007-11-02 | 2012-05-29 | Samsung Electronics Co., Ltd. | Naphthoxazine benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8187766B2 (en) | 2007-11-06 | 2012-05-29 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8227138B2 (en) | 2007-11-02 | 2012-07-24 | Samsung Electronics Co., Ltd. | Phosphorus containing benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8252890B2 (en) | 2007-09-11 | 2012-08-28 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell using the same |
| US8298450B2 (en) | 2007-10-11 | 2012-10-30 | Samsung Electronics Co., Ltd. | Polybenzimidazole-base complex, crosslinked material of polybenzoxazines formed thereof, and fuel cell using the same |
| US8323849B2 (en) | 2007-11-02 | 2012-12-04 | Samsung Electronics Co., Ltd. | Electrolyte membrane containing a crosslinked polybenzoxazine-based compound for fuel cell and fuel cell using the same |
| US8679699B2 (en) | 2006-08-22 | 2014-03-25 | Samsung Sdi Co., Ltd | Membrane electrode assembly for fuel cell and fuel cell employing the same |
-
2000
- 2000-03-24 JP JP2000084468A patent/JP2001270891A/en not_active Withdrawn
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| US8349515B2 (en) | 2005-09-03 | 2013-01-08 | Samsung Sdi Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| US8034508B2 (en) | 2005-09-03 | 2011-10-11 | Samsung Sdi Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| US8426081B2 (en) | 2005-09-03 | 2013-04-23 | Samsung Sdi Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| US8580455B2 (en) | 2006-05-29 | 2013-11-12 | Samsung Sdi Co., Ltd. | Crosslinked polybenzoxazines, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| US8148028B2 (en) | 2006-05-29 | 2012-04-03 | Samsung Sdi Co., Ltd. | Polybenzoxazines, electrolyte membrane comprising the same, and fuel cell employing the electrolyte membrane |
| US8679699B2 (en) | 2006-08-22 | 2014-03-25 | Samsung Sdi Co., Ltd | Membrane electrode assembly for fuel cell and fuel cell employing the same |
| US8252890B2 (en) | 2007-09-11 | 2012-08-28 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell using the same |
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| US8192892B2 (en) | 2007-09-11 | 2012-06-05 | Samsung Electronics Co., Ltd. | Phosphorous containing benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell employing the same |
| US9243012B2 (en) | 2007-09-11 | 2016-01-26 | Samsung Electronics Co., Ltd. | Phosphorous containing benzoxazine-based monomer, or polymer thereof |
| EP2036912A1 (en) | 2007-09-11 | 2009-03-18 | Samsung Electronics Co., Ltd. | Phosphorous containing benzoxazine-based monomer, polymer thererof, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell employing the same |
| US8715881B2 (en) | 2007-09-11 | 2014-05-06 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the same, electrolyte membrane for fuel cell including the same, and fuel cell using the same |
| JP2009068011A (en) * | 2007-09-11 | 2009-04-02 | Samsung Electronics Co Ltd | Phosphorus-containing benzoxazine-based monomer, polymer of phosphorus-containing benzoxazine-based monomer, electrode for fuel cell, electrolyte membrane for fuel cell, and fuel cell |
| KR101015503B1 (en) * | 2007-09-11 | 2011-02-22 | 삼성전자주식회사 | Phosphorous containing benzoxazine-based monomer, polymer thererof, electrode for fuel cell including the sane, electrolyte membrane for fuel cell including the same, and fuel cell employing the same |
| US8298450B2 (en) | 2007-10-11 | 2012-10-30 | Samsung Electronics Co., Ltd. | Polybenzimidazole-base complex, crosslinked material of polybenzoxazines formed thereof, and fuel cell using the same |
| US8512914B2 (en) | 2007-11-02 | 2013-08-20 | Samsung Electronics Co., Ltd. | Phosphorus containing benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8551669B2 (en) | 2007-11-02 | 2013-10-08 | Samsung Electronics Co., Ltd. | Naphthoxazine benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8188210B2 (en) | 2007-11-02 | 2012-05-29 | Samsung Electronics Co., Ltd. | Naphthoxazine benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8323849B2 (en) | 2007-11-02 | 2012-12-04 | Samsung Electronics Co., Ltd. | Electrolyte membrane containing a crosslinked polybenzoxazine-based compound for fuel cell and fuel cell using the same |
| US8808941B2 (en) | 2007-11-02 | 2014-08-19 | Samsung Electronics Co., Ltd. | Naphthoxazine benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8227138B2 (en) | 2007-11-02 | 2012-07-24 | Samsung Electronics Co., Ltd. | Phosphorus containing benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8507148B2 (en) | 2007-11-06 | 2013-08-13 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| US8187766B2 (en) | 2007-11-06 | 2012-05-29 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
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